Compounds for use in optical sensors - Patent Application 20070122997

Abstract

A compound of formula (I), wherein X 1 is C(R 1 )2, Si(R 1 )2 or Ge(R 1 )2, where R 1 is a substituent in each occurrence, and Y 1 is O, S or Se, and Ar 1 is independently in each occurrence an unsubstituted or substituted monocyclic or polycyclic aryl or heteroaryl group, or is absent; B 1 is, independently in each occurrence, a bridging group, f1 and f2 are each 1, g is at least 1, and A, independently in each occurrence, is a monovalent electron-withdrawing group. The compound of formula (I) can be used as an electron-withdrawing material in an organic photoresponsive device.

Description

[Background technology]

[0001] WO 2022 / 129137 discloses compounds of the formula EAG-EDG-EAG, where EDG is a group of formula (II) and each EAG is independently an electron-withdrawing group of formula (III). [ka]

[0002] J. Vollbrecht et al., "Design of narrow bandgap non-fullerene acceptors for photovoltaic applications and investigation of non-geminate recombination dynamics," J. Mater. Chem. C, 2020, 8, 15175-15182, discloses solar cells containing the donor polymer PTB7-Th or PBDBT and the acceptor CETIC-4F (shown below) or COTIC-4F. [ka]

[0003] WO 2021 / 079140 discloses a composition comprising an electron acceptor material and an electron donor material, where the electron acceptor material is of the formula EAG-EDG-EAG, where each EAG is an electron-withdrawing group and EDG is a group of the formula: [ka] [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2022 / 129137 [Patent Document 2] International Publication No. 2021 / 079140 [Non-patent literature]

[0005] [Non-Patent Document 1] J Vollbrecht et al, "Design of narrow bandgap non-fullerene acceptors for photovoltaic applications and investigation of non-geminate recombination dynamics", J.Mater.Chem.C,2020,8,15175-15182 Summary of the Invention [Means for solving the problem]

[0006] The present disclosure provides a compound of formula (I): [ka] wherein: X 1 is C(R 1 )2, Si(R 1 )2 or Ge(R 1 )2, where R 1 is, in each occurrence, a substituent; Y 1 is O, S or Se, Ar 1 is independently in each occurrence an unsubstituted or substituted monocyclic or polycyclic aryl or heteroaryl group, or is absent; B 1 is, independently in each occurrence, a bridging group; f1 and f2 are each independently 1; g is at least 1, A in each occurrence is independently a monovalent electron-withdrawing group.

[0007] Optionally, at least one A is of formula (II): [ka] is an electron-withdrawing group of the formula: G is C=O, C=S SO, SO2, NR 33 or C(R 33 )2, where R 33 CN or COOR 40 where R 40 is, in each occurrence, H or a substituent; R 3 is H or a substituent, Z is independently CN, CF3, or COOR 40 where R 40 is, in each occurrence, H or a substituent; Ar 2 is an unsubstituted or substituted monocyclic or polycyclic aromatic or heteroaromatic ring.

[0008] In some cases, Ar 2 teeth, benzene substituted with at least one CN substituent; and unsubstituted or substituted monocyclic or polycyclic heteroaromatic groups is selected from.

[0009] Optionally, the group of formula (II) is of formula (IIa): [ka] wherein each X 7 ~X 10 is an independent CR 12 or N and R 12 is H or C in each occurrence 1~20 are substituents selected from hydrocarbyls and electron-withdrawing groups, provided that X 7 ~X 10 Each of these is CR 12 If there is at least one R 12 is CN.

[0010] Optionally, the group of formula (II) is of formula (IIb): [ka] wherein Ar 3 is an unsubstituted or substituted monocyclic or polycyclic aromatic or heteroaromatic group.

[0011] In some cases, Ar 2 is unsubstituted or substituted benzene.

[0012] In some cases, B 1 is selected from unsubstituted or substituted furan; unsubstituted or substituted thiophene; or fused analogs thereof.

[0013] In some cases, B 1 is of formula (III): [ka] where Y 2 is O, S or Se, and Ar 4 is an unsubstituted or substituted monocyclic or polycyclic aromatic or heteroaromatic group.

[0014] In some cases, Ar 3 is of formula (IIIa): [ka] where R 8 is H or a substituent group at each occurrence.

[0015] The present disclosure provides compositions comprising the compounds described herein and an electron donating material.

[0016] The present disclosure provides formulations comprising a compound or composition described herein dissolved or dispersed in one or more solvents.

[0017] The present disclosure provides an organic photoresponsive device comprising an anode, a cathode, and a photoactive layer disposed between the anode and the cathode, wherein the photoactive layer comprises a composition described herein.

[0018] The present disclosure provides a light sensor including a light source and an organic photodetector as described herein, wherein the organic photodetector is configured to detect light emitted from the light source. In some cases, the light source emits light having a peak wavelength greater than 1000 nm.

[0019] The disclosed technology and the accompanying drawings illustrate several implementations of the disclosed technology. [Brief explanation of the drawings]

[0020] [Figure 1] 1 is a schematic diagram of an organic photoresponsive device according to some embodiments.

[0021] The drawings are not drawn to scale and have various perspectives and viewpoints. The drawings are of several implementations and examples. Furthermore, some components and / or operations may be separated into different blocks or combined into a single block for the purpose of illustrating some embodiments of the disclosed technology. Moreover, while the technology is susceptible to various modifications and alternative forms, specific embodiments are shown by way of example in the drawings and are described in detail below. However, the intention is not to limit the technology to the particular implementations described. On the contrary, the technology is intended to encompass all modifications, equivalents, and alternatives falling within the scope of the technology as defined by the appended claims. DETAILED DESCRIPTION OF THE INVENTION

[0022] Unless the context clearly dictates otherwise, throughout the specification and claims, words like "comprise," "comprising," and the like, should be construed in an inclusive sense, i.e., "including but not limited to," as opposed to an exclusive or exhaustive sense. Furthermore, the words "herein," "above," "below," and words of similar import, when used in this application, refer to this application as a whole and not to any particular portion of this application. Where the context permits, words in the detailed description using the singular or plural may also include the plural or singular, respectively. The word "or" in connection with a list of two or more items encompasses all of the following interpretations of that word: any of the items in the list, all of the items in the list, and any combination of the items in the list. As used in this application, a reference to a layer "on" another layer means that the layers may be in direct contact or that there may be one or more intervening layers. As used in this application, a reference to a layer "on" another layer means that the layers are in direct contact. A reference to a particular atom includes any isotopes of that atom unless otherwise specified.

[0023] The teachings of the technology provided herein may be applied to other systems, not necessarily the systems described below. Elements and operations of the various examples described below may be combined to provide further implementations of the technology. Some alternative implementations of the technology may include fewer elements as well as additional elements relative to the implementations described below.

[0024] These and other changes can be made to the present technology in light of the following detailed description. The description describes particular examples of the technology and sets forth the best mode contemplated, but no matter how detailed the description appears, the technology can be practiced in many ways. As noted above, specific terms used when describing particular features or aspects of the technology should not be construed to mean that the terms have been redefined herein to be limited to any particular characteristic, feature, or aspect of the relevant technology. In general, the terms used in the following claims should not be construed to limit the technology to the specific examples disclosed herein, unless the detailed description section explicitly defines such terms. Thus, the actual scope of the present technology encompasses not only the disclosed examples, but also all equivalent ways of practicing or implementing the claimed technology.

[0025] In order to reduce the number of claims, certain aspects of the technology are presented below in certain claim forms, but applicants contemplate various aspects of the technology in any number of claim forms.

[0026] In the following description, for purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of implementations of the disclosed technology. However, it will be apparent to one skilled in the art that embodiments of the disclosed technology may be practiced without some of these specific details.

[0027] Donor group D The compounds of formula (I) may contain an electron donating group D: [ka] Including, X 1 is C(R 1 )2, Si(R 1 )2 or Ge(R 1 )2, where R 1 is a substituent at each occurrence.

[0028] Y 1is O, S or Se.

[0029] Ar 1 is independently in each occurrence an unsubstituted or substituted monocyclic or polycyclic aryl or heteroaryl group, or is absent.

[0030] g is at least 1, preferably 1, 2 or 3.

[0031] Each of the electron-withdrawing groups A in Formula (I) has a lowest unoccupied molecular orbital (LUMO) level that is deeper (i.e., further from vacuum) than the donor group D in Formula (I), preferably at least 1 eV deeper. The LUMO levels of the electron-withdrawing group A and the electron-donating group D can be determined by modeling the LUMO levels of these groups where each bond to an adjacent group is replaced with a bond to a hydrogen atom. Modeling can be performed using Gaussian09 software, available from Gaussian, using Gaussian09 with B3LYP (function) and LACVP* (basis set).

[0032] Preferably, the compounds of formula (I) have a peak absorption wavelength of greater than 1000 nm, optionally at least 1200 nm, preferably less than 1800 nm.

[0033] Preferably, R in each occurrence 1 teeth, One or more non-adjacent C atoms are O, S, NR 17 can be replaced by R 17 C 1~12 Hydrocarbyl, COO or CO, wherein one or more H atoms of the alkyl may be replaced by F. 1~20 alkyl; and an aromatic or heteroaromatic group, preferably C, which is unsubstituted or substituted with one or more substituents; 6~20 Aryl, more preferably phenyl are independently selected from

[0034] If present, the aromatic or heteroaromatic group R 1 The substituents in are preferably the substituents R 11 where R 11 represents, independently in each occurrence, F, Cl, Br, CN, NO2, and C 1~20 alkyl, wherein one or more non-adjacent C atoms are O, S, NR 17 where R 17 is C 1~12 Hydrocarbyl, COO or CO, and one or more H atoms of the alkyl may be replaced by F.

[0035] R 17 is optionally unsubstituted or substituted with one or more C 1~6 Alkyl-substituted C 1~12 It is alkyl or phenyl.

[0036] A "non-terminal C atom" of an alkyl group as used anywhere in this specification means a C atom other than the C atom of the methyl group at the end of an n-alkyl chain or the C atom of the methyl group at the end of a branched alkyl chain.

[0037] When the terminal C atom of a group described anywhere herein is substituted, the resulting group may be an anionic group comprising a countercation, for example an ammonium or metal countercation, preferably an ammonium or alkali metal cation.

[0038] A C atom of an alkyl substituent that is replaced by another atom or group as described anywhere herein is preferably a non-terminal C atom, and the resulting substituent is preferably non-ionic.

[0039] Each Ar 1 may independently be present or absent. In embodiments where Ar1 is absent, the group D has the formula D-1: [ka] wherein R 2is, in each occurrence, independently H or a substituent, and optionally H or the substituent R 11 Preferably, each R 2 is H.

[0040] In some cases, only one Ar 1 There is a group.

[0041] In some cases, both Ar 1 In this case, Ar 1 The groups may be the same or different. Preferably, Ar 1 are independently selected from furan, thiophene; furofuran; thienothiophene; and furothiophene. 1 The substituents of, when present, are the same as those of the above-mentioned substituents R 11 may be selected from:

[0042] Crosslinking Unit Crosslinking unit B 1 are preferably each selected from vinylene, arylene, and heteroarylene. The arylene and heteroarylene groups are preferably monocyclic or bicyclic groups, each of which may be unsubstituted or substituted with one or more substituents.

[0043] Preferably, each B 1 contains at least one arylene or heteroarylene group, more preferably at least one heteroarylene group.

[0044] Exemplary Monocyclic Aromatic and Heteroaromatic Groups B 1 are benzene, thiophene and furan, each of which may be unsubstituted or may contain one or more substituents, optionally one or more substituents R as described below. 8 may be substituted with

[0045] Exemplary Bicyclic Groups B 1 is selected from formulas (III) and (IV). [Table 1] In the formula, Ar 4 is an unsubstituted or substituted monocyclic aromatic or heteroaromatic group, preferably benzene; thiophene; furan; pyridine; pyrazine; or piperidine, each of which may be unsubstituted or substituted with one or more substituents, and optionally one or more substituents R as described below. 8 may be substituted with

[0046] Optionally, a heteroarylene group B 1 is selected from units of formulae (VIa) to (VIo). [Table 2] TIFF2026506000000015.tif32143In formula, R 55 is H or a substituent, optionally H or C 1~20 is a hydrocarbyl group, R 8 is, in each occurrence, independently H or a substituent, preferably H or F; CN; NO2; one or more non-adjacent C atoms are O, S, or NR 6 , COO, or CO, and one or more H atoms of the alkyl may be replaced by F. 1~20 alkyl; phenyl which is unsubstituted or substituted with one or more substituents; and -B(R 14 )2(wherein, R 14 is, in each occurrence, a substituent, and C 1~20 The substituent is selected from the group consisting of alkyl, aryl, aryl, aryl groups, and alkyl groups.

[0047] Phenyl group R 8 The substituents of, when present, are the same as those of the above-mentioned substituents R 11 may be selected from:

[0048] R 6 is H or a substituent, preferably H or C 1~20 It is a hydrocarbyl group.

[0049] C as described anywhere in this specification1~20 The hydrocarbyl group is C 1~20 alkyl; unsubstituted phenyl; and one or more C 1~12 It may be selected from phenyl substituted with an alkyl group.

[0050] R in formula (VIa), (VIb) and (VIc) 8 The groups may be linked to one or more substituents, optionally F; CN; NO; one or more non-adjacent C atoms may be O, S, NR 6 , COO, or CO, and one or more H atoms of the alkyl may be replaced by F. 1~20 Bicyclic rings may be formed which may be substituted with alkyl.

[0051] R 8 is preferably H, C 1~20 Alkyl or C 1~19 It is an alkoxy.

[0052] R in formula (VIa), (VIb) and (VIc) 8 The groups may be linked to form an optionally substituted bicyclic ring.

[0053] Electron-withdrawing group A Each monovalent acceptor group A may be independently selected from any such unit known to those skilled in the art.

[0054] The A groups in the compounds of formula (I) may be the same or different, preferably the same.

[0055] Exemplary monovalent acceptor groups include, but are not limited to, groups of formulae (IXa)-(IXq): [Table 3] TIFF2026506000000017.tif202146TIFF2026506000000018.tif26153

[0056] U is a 5- or 6-membered ring that is unsubstituted or substituted with one or more substituents and that may be fused to one or more further rings.

[0057] G is C=O, C=S SO, SO2, NR 33 or C(R 33 )2, where R 33 CN or COOR 40 G is preferably C=O or SO2, more preferably C=O.

[0058] The N atom of formula (IXe) may be unsubstituted or substituted.

[0059] R 3 is H or a substituent, preferably H or C 1~12 alkyl, wherein one or more non-adjacent C atoms are O, S, NR 6 , COO or CO, and one or more H atoms of the alkyl may be substituted with F; and unsubstituted or with F and C 1~12 alkyl, and one or more non-adjacent C atoms may be substituted with one or more substituents selected from O, S, NR 6 , COO or CO, and optionally phenyl.

[0060] Most preferably, R 3 is H.

[0061] J is O or S, preferably O.

[0062] R 13 represents, at each occurrence, a substituent, optionally C 1~12 alkyl, where one or more non-adjacent C atoms are O, S, NR 6 , COO or CO, and one or more H atoms of the alkyl may be replaced by F.

[0063] R 15represents, independently in each occurrence, H; F; one or more non-adjacent C atoms are O, S, or NR 6 , COO, or CO, and one or more H atoms of the alkyl may be replaced by F. 1~12 Alkyl; unsubstituted or F and C 1~12 alkyl, and one or more non-adjacent C atoms may be substituted with one or more substituents selected from O, S, NR 6 , an aromatic group which may be substituted with COO or CO, optionally phenyl, or [ka] It may be a group selected from:

[0064] R 16 is H or a substituent, preferably -(Ar 5 ) w (In the formula, Ar 5 is, in each occurrence, independently an unsubstituted or substituted aryl or heteroaryl group, preferably thiophene, and w is 1, 2, or 3; [ka] and One or more non-adjacent C atoms are O, S, or NR 6 , COO, or CO, and one or more H atoms of the alkyl may be replaced by F. 1~12 The substituent is selected from alkyl.

[0065] Ar 6 is a 5-membered heteroaromatic group, preferably thiophene or furan, which is unsubstituted or substituted with one or more substituents.

[0066] Ar 5 and Ar 6 If present, the substituents may be O, S, NR 6 , COO, or CO, and one or more H atoms of the alkyl may be replaced by F.1~12 It may be selected from alkyl.

[0067] T 1 , T 2 and T 3 each independently represents an aryl or heteroaryl ring, optionally benzene, which may be fused to one or more further rings. 1 , T 2 and T 3 The substituents of R, when present, 25 In a preferred embodiment, T 3 is a benzothiadiazole.

[0068] Z 1 is N or P.

[0069] Ar 8 is unsubstituted or has one or more substituents, optionally one or more non-H substituents R 3 is substituted with B 1 or B 2 Aromatic C atoms and B 1 or B 2 is a fused heteroaromatic group attached to a boron substituent of

[0070] Preferred groups A are B 1 is a group having a non-aromatic carbon-carbon bond directly attached to

[0071] Preferably, at least one group A, preferably both groups A, has the formula (II): [ka] is a group of the formula G is as defined above, preferably C=O or SO2, more preferably C=O; R 3 is as above, Ar 2is an unsubstituted or substituted monocyclic or fused aromatic or heteroaromatic group, preferably a benzene or monocyclic or bicyclic heteroaromatic group having only C or N ring atoms, Each Z is independently CN, CF3, or COOR 40 where R 40 is, in each occurrence, H or a substituent, preferably H or C 1~20 is a hydrocarbyl group. Preferably, each Z is the same. Preferably, each Z is CN.

[0072] Ar 2 Ar may be unsubstituted or substituted with one or more substituents. 2 The substituents of are preferably groups R as defined above. 11 is selected from.

[0073] Optionally, the group of formula (II) is of formula (IIa): [ka] wherein each X 7 ~X 10 is an independent CR 12 or N and R 12 is H or C in each occurrence 1~20 The substituent is selected from hydrocarbyl and electron-withdrawing groups. Preferably, the electron-withdrawing group is F, Cl, Br or CN, more preferably F, Cl or CN, and most preferably CN.

[0074] C 1~20 Hydrocarbyl group R 12 is C 1~20 alkyl; unsubstituted phenyl; and one or more C 1~12 It may be selected from phenyl substituted with an alkyl group.

[0075] In a particularly preferred embodiment, X 7 ~X 10 Each of the 12 and each R 12are independently selected from H or an electron withdrawing group, preferably H, F or CN. According to this embodiment, X 8 and X 9 R 12 is an electron withdrawing group, preferably F or CN.

[0076] Optionally, the group of formula (II) is of formula (IIb): [ka] wherein Ar 3 is an unsubstituted or substituted monocyclic or polycyclic aromatic or heteroaromatic group. 3 is benzene, which is unsubstituted or substituted with one or more substituents. 3 The substituents of R 11 , more preferably the above R 12 may be selected from:

[0077] Exemplary groups of formula (IXd) include: [ka]

[0078] Exemplary groups of formula (IXe) include: [ka]

[0079] Exemplary groups of formula (IXq) are: [ka]

[0080] Exemplary groups of formula (IXg) are: [ka]

[0081] Exemplary groups of formula (IXj) are: [ka]

[0082] where Ak is a group in which one or more C atoms are O, S, NR 6 C, which may be substituted by CO or COO 1~12 An is an anion, optionally -SO3 - and each benzene ring is independently unsubstituted or R 3 and is substituted with one or more substituents selected from the substituents described with reference to

[0083] Exemplary groups of formula (IXm) are: [ka]

[0084] Exemplary groups of formula (IXn) are: [ka]

[0085] The group of formula (IXo) is a group of formula -B(R 14 )2 groups substituted with a bridging group B 1 or B 2 wherein R 14 is a substituent in each occurrence, and optionally C 1~20 is a hydrocarbyl group, and → is a boron atom -B(R 14 )2, and --- is a CC bond between formula (IXo) and the bridging group.

[0086] In some cases, R 14 is C 1~12 alkyl; unsubstituted phenyl; and one or more C 1~12 phenyl substituted with an alkyl group.

[0087] Group of formula (IXo), B 1 or B 2 Group and B1 or B 2 B(R 14 ) Two substituents may be linked together to form a 5- or 6-membered ring.

[0088] Optionally, the group of formula (IXo) is selected from: [ka]

[0089] Organic Electronic Devices 1 shows an organic photoresponsive device, preferably an organic photodetector, according to some embodiments of the present disclosure. The organic photoresponsive device includes a cathode 103, an anode 107, and a bulk heterojunction layer 105 disposed between the anode and the cathode. The organic photoresponsive device may be supported on a substrate 101, optionally a glass or plastic substrate.

[0090] The bulk heterojunction layer comprises or consists of a compound of formula (I) and an electron donating compound. The bulk heterojunction layer comprises one or more additional materials, such as one or more additional electron donating materials and / or one or more additional electron withdrawing materials.

[0091] In some embodiments, the weight ratio of electron donating material(s) to electron withdrawing material(s) is from about 1:0.5 to about 1:2, preferably from about 1:1.1 to about 1:2.

[0092] Preferably, the or each electron donor material has a type II interface with the or each electron withdrawing material, i.e., the or each electron donor material has a HOMO and LUMO that are shallower than the corresponding HOMO and LUMO levels of the or each electron withdrawing material. Preferably, the compound of formula (I) has a HOMO level that is at least 0.05 eV deeper, and optionally at least 0.10 eV deeper, than the HOMO of the electron donor material.

[0093] Optionally, the gap between the HOMO level of the electron donating material and the LUMO level of the compound of formula (I) is less than 1.4 eV.

[0094] Each of the anode and cathode may independently be a single conductive layer or may include multiple layers.

[0095] At least one of the anode and cathode is transparent so that light incident on the device can reach the bulk heterojunction layer. In some embodiments, both the anode and the cathode are transparent. The transmittance of the transparent electrode can be selected depending on the emission wavelength of the light source used with the organic photodetector.

[0096] 1 shows a configuration in which the photoresponsive device includes a bulk heterojunction photoactive layer 105. In other embodiments, the photoactive layer includes an electron-withdrawing sublayer comprising or consisting of a compound of Formula (I) disposed between the anode and the cathode, and an electron-donating sublayer comprising or consisting of one or more electron-donating materials disposed between the anode and the electron-withdrawing layer and in direct contact with the electron-withdrawing layer.

[0097] 1 shows an arrangement in which the cathode is disposed between the substrate and the anode. In other embodiments, the anode may be disposed between the cathode and the substrate.

[0098] Organic photoresponsive devices may include layers other than an anode, a cathode, and a photoactive layer. In some embodiments, a hole transport layer and / or an electron blocking layer is disposed between the anode and the photoactive layer. In some embodiments, an electron transport layer and / or a hole blocking layer is disposed between the cathode and the photoactive layer. In some embodiments, a work function modifying layer is disposed between the photoactive layer and the anode and / or between the photoactive layer and the cathode.

[0099] The substrate may be, but is not limited to, a glass or plastic substrate. The substrate may be an inorganic semiconductor. In some embodiments, the substrate may be silicon. For example, the substrate may be a silicon wafer. A substrate is transparent if, in use, incident light passes through the substrate and the electrodes supported by the substrate.

[0100] Electron-donating materials Exemplary electron donating materials for the photoactive layers described herein are disclosed, for example, in WO 2013 / 051676, the contents of which are incorporated herein by reference.

[0101] The electron donating material may be a non-polymeric or polymeric material.

[0102] In a preferred embodiment, the electron donating material is an organic conjugated polymer, which can be a homopolymer or a copolymer, including alternating, random, or block copolymers. The conjugated polymer is preferably a donor-acceptor polymer that contains alternating electron donating and electron withdrawing repeat units.

[0103] Amorphous or semi-crystalline conjugated organic polymers are preferred.

[0104] More preferably, the electron donating polymer is a conjugated organic polymer with a low bandgap, typically between 2.5 eV and 1.5 eV, preferably between 2.3 eV and 1.8 eV.

[0105] In some cases, the electron donating polymer has a HOMO level of 5.5 eV or less from the vacuum level. In some cases, the electron donating polymer has a HOMO level of at least 4.1 eV from the vacuum level. Exemplary electron donating polymers include polyacenes, polyanilines, polyazulenes, polybenzofurans, polyfluorenes, polyfurans, polyindenofluorenes, polyindoles, polyphenylenes, polypyrazolines, polypyrenes, polypyridazines, polypyridines, polytriarylamines, poly(phenylene vinylenes), poly(3-substituted thiophenes), poly(3,4-disubstituted thiophenes), polyselenophenes, poly(3-substituted selenophenes), poly(3,4-disubstituted selenophenes). ), poly(bisthiophenes), poly(terthiophenes), poly(bisselenophenes), poly(terselenophenes), polythieno[2,3-b]thiophenes, polythieno[3,2-b]thiophenes, polybenzothiophenes, polybenzo[1,2-b:4,5-b']dithiophenes, polyisothianaphenes, poly(monosubstituted pyrroles), poly(3,4-disubstituted pyrroles), poly-1,3,4-oxadiazoles, polyisothianaphthenes, derivatives and copolymers thereof may be mentioned.

[0106] Preferred examples of donor polymers are copolymers of polyfluorenes and polythiophenes, each of which may be substituted, and polymers containing benzothiadiazole-based and thiophene-based repeat units, each of which may be substituted.

[0107] The donor polymer is preferably a donor-acceptor (DA) copolymer comprising donor repeat units and acceptor repeat units.

[0108] Preferred donor units are those containing one or more substituents R 11 thiophenes optionally substituted with: and repeat units of formula (X), (XII) and (XII): [ka] is selected from: Y at each occurrence Aare independently O, S or NR 55 and Z for each occurrence A are O, CO, S, NR 55 or C(R 54 )2 and R 51 , R 54 and R 55 is independently in each occurrence H or a substituent group.

[0109] In some cases, R 51 represents, independently in each occurrence, H; F; one or more non-adjacent C atoms are O, S, or NR 2 , COO, or CO, and one or more H atoms of the alkyl may be replaced by F. 1~20 alkyl; and an aromatic or heteroaromatic group Ar which is unsubstituted or substituted with one or more substituents. 3 is selected from.

[0110] In some embodiments, Ar 3 Ar may be an aromatic group, for example, phenyl. 3 If present, one or more substituents may be substituted by O, S, NR 6 , COO or CO, and one or more H atoms of the alkyl may be replaced by F. 1~12 It may be selected from alkyl.

[0111] Preferably, each R 51 is H.

[0112] Preferably, each R 54 teeth, H; F; One or more non-adjacent C atoms are O, S, NR 17 , which may be replaced by CO or COO, 17 C 1~12 Hydrocarbyl, C 1~20 A straight-chain, branched or cyclic C alkyl group in which one or more H atoms may be replaced by F. 1~20 alkyl; and Ak is a group in which one or more non-adjacent C atoms are O, S, NR 6 , C which can be replaced by CO or COO 1~20 is an alkylene chain, u is 0 or 1, and Ar 7 is independently in each occurrence an aromatic or heteroaromatic group that is unsubstituted or substituted with one or more substituents, and v is at least 1, and optionally 1, 2, or 3, 7 )v base is selected from the group consisting of:

[0113] Ar 7 The substituents, if present, are preferably F; Cl; NO; CN; and one or more non-adjacent C atoms are O, S, NR 6 , C, which may be replaced by CO or COO, and one or more H atoms may be replaced by F 1~20 alkyl. Preferably, Ar 7 is phenyl.

[0114] Preferably, R 55 is H or C 1~20 is a hydrocarbyl group, [ka] In the formula, R 18 and R 19 are each independently H; F; C in which one or more non-adjacent non-terminal C atoms can be replaced by O, S, COO or CO, and one or more H atoms of the alkyl can be replaced by F; 1~12 Alkyl; unsubstituted or containing F and C 1~12 alkyl, and one or more non-adjacent non-terminal C atoms may be substituted by O, S, COO or CO, optionally phenyl or a 5-membered heteroaromatic group. [ka] In the formula, Y 3 is O, S or Se, preferably S, and R 5is, in each occurrence, H or a substituent, more preferably H or the substituent R 11 and most preferably H, and Q is C(R 21 )2 or Si(R 21 )2, where R 21 is, in each occurrence, a substituent, preferably C 1~20 alkyl, wherein one or more non-adjacent C atoms are O, S, NR 17 where R 17 is C 1~12 hydrocarbyl, COO or CO, wherein one or more H atoms of the alkyl may be replaced by F, an aromatic or heteroaromatic group which is unsubstituted or substituted by one or more substituents, preferably C 6~20 Aryl, more preferably phenyl. An aromatic or heteroaromatic group R 21 The substituents of R 11 may be selected from:

[0115] Preferred acceptor units include one or more substituents R 11 and a repeat unit of formula (XIII): [ka] and benzothiadiazoles optionally substituted by, wherein R 2 is H or a substituent, and Y 4 is O, S or Se, preferably S.

[0116] R 2 is preferably H; a terminal C atom or NR 2 C other than C atoms bonded to N 1~12 C, in which one or more C atoms of the alkyl may be replaced by O, S, CO or COO 1~12 alkyl; or an aromatic or heteroaromatic group, preferably C 6~12 Aryl groups, more preferably phenyl, may be unsubstituted or substituted with one or more substituents.

[0117] If present, the aromatic or heteroaromatic group R 2 The substituents in are preferably those of the above R 11 is selected from.

[0118] fullerene In some embodiments, the compound of Formula (I) is the only electron-withdrawing material in an electron-withdrawing sublayer or bulk heterojunction layer described herein.

[0119] In some embodiments, the electron-withdrawing layer or bulk heterojunction layer comprises a compound of Formula (I) and one or more additional electron-withdrawing materials. A preferred additional electron-withdrawing material is fullerene. The weight ratio of the compound of Formula (I) to fullerene acceptor can be in the range of about 1:0.1 to 1:1, preferably in the range of about 1:0.1 to 1:0.5.

[0120] Fullerenes include, but are not limited to, C 60 , C 70 , C 76 , C 78 and C 84 It can be selected from fullerenes or derivatives thereof, including but not limited to phenyl-C 61 -Butyric acid methyl ester (C 60 PCBM), PCBM-type fullerene derivatives, TCBM-type fullerene derivatives (e.g., tolyl-C 61 -Butyric acid methyl ester (C 60 TCBM), and ThCBM-type fullerene derivatives (e.g., thienyl-C 61 -Butyric acid methyl ester (C 60 ThCBM).

[0121] The fullerene derivative has the formula (V): [ka] where A together with the CC group of the fullerene forms a monocyclic or fused ring group which may be unsubstituted or substituted with one or more substituents.

[0122] Exemplary fullerene derivatives include those of formulae (Va), (Vb), and (Vc). [Table 4] In the formula, R 20 ~R 32 are each independently H or a substituent.

[0123] Substituent R 20 ~R 32 is optionally independently at each occurrence an aryl or heteroaryl which is unsubstituted or substituted by one or more substituents, optionally phenyl; and one or more non-adjacent C atoms are O, S, NR 6 , C, which may be replaced by CO or COO, and one or more H atoms may be replaced by F 1~20 alkyl.

[0124] The aryl or heteroaryl substituents, if present, are C 1~12 alkyl, and one or more non-adjacent C atoms may be selected from O, S, NR 6 , CO or COO, and one or more H atoms may be replaced by F.

[0125] formulation The photoactive layer can be formed by any process, including, but not limited to, thermal evaporation and solution deposition.

[0126] Preferably, the electron-withdrawing sublayer or bulk heterojunction layer is formed by depositing a formulation comprising a compound of Formula (I) and any other components of the layer (including, in the case of a bulk heterojunction layer, one or more electron-donating materials dissolved or dispersed in a solvent or a mixture of two or more solvents), followed by evaporation of the solvent(s). The formulation can be deposited by any coating or printing method, including, but not limited to, spin coating, dip coating, roll coating, spray coating, doctor blade coating, wire bar coating, slit coating, inkjet printing, screen printing, gravure printing, and flexographic printing.

[0127] The formulation may comprise a mixture of two or more solvents, preferably a mixture comprising at least one benzene substituted with one or more of the substituents described above and one or more further solvents, the one or more further solvents being esters, optionally alkyl or aryl esters of alkyl or aryl carboxylic acids, optionally C 1~10 The solvent may be selected from alkyl benzoates, benzyl benzoates, or dimethoxybenzenes. In a preferred embodiment, a mixture of trimethylbenzene and benzyl benzoate is used as the solvent. In another preferred embodiment, a mixture of trimethylbenzene and dimethoxybenzene is used as the solvent.

[0128] In addition to the electron-withdrawing material, the electron-donating material, and one or more solvents, the formulation may contain further ingredients, such as adhesives, defoamers, deaerators, thickeners, diluents, adjuvants, flow improvers, colorants, dyes or pigments, sensitizers, stabilizers, nanoparticles, surface-active compounds, lubricants, wetting agents, dispersants, and suppressors.

[0129] The photoactive layer is formed on one of the anode and cathode of the organic photoresponsive device, and the other of the anode and cathode is formed on the photoactive layer.

[0130] Purpose The circuit may include the OPD connected to one or more of a voltage source for applying a reverse bias to the device; a device for measuring the photocurrent; and an amplifier configured to amplify the output signal of the OPD. The voltage applied to the photodetector may be variable. In some embodiments, the photodetector may be continuously biased during use.

[0131] In some embodiments, the photodetector system includes a plurality of photodetectors (such as a camera image sensor) as described herein.

[0132] In some embodiments, a sensor can include an OPD described herein and a light source, where the OPD is configured to receive light emitted from the light source. In some embodiments, the light source has a peak wavelength of at least 1000 nm or at least 1200 nm, optionally in the range of 1000-1500 nm.

[0133] In some embodiments, the light from the light source may or may not be modified before reaching the OPD, for example, the light may be reflected, filtered, downconverted, or upconverted before reaching the OPD.

[0134] The organic photoresponsive devices described herein may be organic photovoltaic devices or organic photodetectors. The organic photodetectors described herein can be used in a wide range of applications, including, but not limited to, detecting the presence and / or intensity of ambient light, as well as in sensors comprising organic photodetectors and light sources. The photodetector may be configured such that light emitted from a light source is incident on the photodetector, and changes in the wavelength and / or intensity of the light can be detected due to, for example, absorption, reflection, and / or emission of light by an object, such as a target material in a sample, placed in the light path between the light source and the organic photodetector. The sample may be a non-biological sample, such as a water sample, or a biological sample collected from a human or animal subject. The sensor may be, but is not limited to, a gas sensor, a biosensor, an X-ray imager, an image sensor such as a camera image sensor, a motion sensor (e.g., for use in security applications), a proximity sensor, or a fingerprint sensor. A 1D or 2D photosensor array may comprise a plurality of the photodetectors described herein in an image sensor. The light detector may be configured to detect light emitted from a target analyte that emits light when illuminated by a light source or that is bound to a light emitting tag that emits light when illuminated by a light source. The light detector may be configured to detect the wavelength of light emitted by the target analyte or its bound light emitting tag.

[0135] The detection surface area of ​​the OPDs described herein can be selected according to the desired application. In some cases, the OPDs described herein have a detection surface area of ​​about 3 cm 2 Less than 2cm 2 Less than 1cm 2 Less than 0.75cm 2 Less than 0.5cm 2 Less than or about 0.25 cm 2 Optionally, each OPD may be part of an OPD array, and each OPD may have an area described herein, optionally less than 1 mm 2 Area less than 0.5 μm 2 ~900μm 2 are pixels of the array having an area in the range

[0136] [Example] measurement Unless otherwise stated, the HOMO and LUMO levels of the materials as described herein are as measured by square wave voltammetry (SWV).

[0137] In the SWV method, the potential between the working and reference electrodes is linearly swept over time while the current at the working electrode is measured. The differential current between the forward and reverse pulses is plotted as a function of potential to obtain a voltammogram. Measurements can be performed using a CHI 660D potentiostat.

[0138] An apparatus for measuring HOMO or LUMO energy levels by SWV may include a cell containing 0.1 M tertiary butylammonium hexafluorophosphate in acetonitrile; a 3 mm diameter glassy carbon working electrode; a platinum counter electrode; and a leak-tight Ag / AgCl reference electrode.

[0139] Ferrocene is added directly to the existing cell at the end of the experiment for calculation purposes, where potentials are determined for the oxidation and reduction of ferrocene relative to Ag / AgCl using cyclic voltammetry (CV).

[0140] The sample is dissolved in toluene (3 mg / ml) and spun directly onto a glassy carbon working electrode at 3000 rpm.

[0141] LUMO = 4.8 - E ferrocene (peak-to-peak average) - E reduced sample (peak maximum).

[0142] HOMO = 4.8 - E ferrocene (peak-to-peak average) + E oxidation of sample (peak maximum).

[0143] A typical SWV experiment is performed at a frequency of 15 Hz; amplitude of 25 mV and incremental steps of 0.004 V. Results are calculated from three freshly spun film samples for both HOMO and LUMO data.

[0144] Unless otherwise stated, absorption spectra were measured using a Cary 5000 UV-VIS-NIR spectrometer. Measurements were performed from 175 nm to 3300 nm using a PbSmart NIR detector for extended photometric range with variable slit widths (down to 0.01 nm) for optimal control of data resolution.

[0145] Unless otherwise stated, absorption values ​​are for solutions. Absorption data is obtained by measuring the intensity of transmitted radiation through a solution sample. The absorption intensity is plotted against the incident wavelength to generate an absorption spectrum. A method for measuring absorption may involve measuring a 15 mg / ml solution in a quartz cuvette and comparing it to a cuvette containing only solvent.

[0146] Unless otherwise stated, the solution absorption data provided herein was measured in toluene solution.

[0147] synthesis As mentioned above, Ar 1 Compounds of formula (I) having a donor group D-1 where R' is C 1~12 The alkyl groups can be prepared according to the following general scheme 1:

[0148] General Scheme 1 [ka]

[0149] At least one Ar 1 The donor group D, in which is present, can be prepared according to general scheme 2, the general approaches described in JP 2015 / 183032 and WO 2021 / 079140, the contents of which are incorporated herein by reference, or according to general scheme 3, the publications mentioned within the scheme are incorporated herein by reference.

[0150] General Scheme 2 [ka]

[0151] General Scheme 3 [ka]

[0152] Compound Example 1 was prepared according to the following reaction scheme: Compound Example 1 [ka]

[0153] Intermediate 2 Intermediate 1 of compound 1 (1.55 g, 2.32 mmol) was dissolved in anhydrous THF (30 mL) and then cooled to −10° C. in an ice / salt bath. The mixture was flushed with N for 15 minutes. N-Bromosuccinimide (0.866 g, 4.87 mmol) was added portionwise to maintain the temperature at −10° C. After the addition was complete, the reaction vessel was wrapped in aluminum foil and stirred under N for 2 hours. NaSO (20 mL) was added to quench any remaining NBS, and the mixture was then diluted with n-heptane (30 mL). The organic phase was washed with saturated water (2 × 40 mL), then brine (40 mL), and dried over MgSO. The solid was removed by filtration, and the solvent was removed under reduced pressure to give intermediate 2 of compound 1 (1.91 g, 99%). The product was used directly in the next step without further purification. HPLC purity = 99.18%.

[0154] 1 H NMR(600 MHz,CDCl3):δ [ppm] 6.96(s,2H),6.86(t,J=1.2 Hz,2H),6.71(d,J=1.2 Hz,2H),2.47(t,J=7.6 Hz,8H),1.51(septet,J=7.6 Hz,8H),1.30-1.24(m,24H),0.89-0.85(m,12H). LCMS m / z 825.2799 [M+H] + . Intermediate 4 A solution of bromothiophene 3 (10.0 g, 19.3 mmol) in anhydrous THF (160 mL) was cooled to −78°C and then flushed with N2 for 15 minutes. n-Butyllithium (2.5 M in hexanes, 8.47 mL, 21.2 mmol) was added dropwise to the mixture, ensuring the internal temperature did not exceed −72°C. The reaction was stirred at −78°C for 2 hours, after which neat 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4.70 mL, 23.1 mmol) was added dropwise, ensuring the internal temperature did not exceed −72°C. The reaction was stirred at −78°C for an additional hour, then allowed to warm to room temperature and stirred for an additional 16 hours. The reaction was cooled to 0°C and quenched by the dropwise addition of 1 M aqueous HCl (approximately 50 mL) to maintain the internal temperature at <2°C. After complete quenching, the mixture was allowed to warm to room temperature. Water (150 mL) and n-heptane (200 mL) were added, and the organic phase was separated and washed with water (2 × 150 mL) and then brine (150 mL). The organic layer was dried over MgSO, filtered, and the solvent was evaporated under reduced pressure to give intermediate 4 of compound 1 (10.94 g, containing residual solvent and protonated thiophene) as a pale orange oil. NMR purity = 84%.

[0155] 1 H NMR(600 MHz,CDCl3):δ [ppm] 6.94(s,1H),5.55(s,1H),3.93(d,J=5.93 Hz,2H),3.75(d,J=10.9 Hz,2H),3.62(d,J=10.9 Hz,2H),1.80-1.74(m,1H),1.50-1.44(m,2H),1.34-1.26(m,42H),0.91(t,J=6.9 Hz,8H),0.81(s,3H). LCMS m / z 656.4246 [M+H] + . Intermediate 5 Intermediate 2 of compound 1 (1.90 g, 2.30 mmol) and intermediate 4 of compound 1 (3.24 g, 5.75 mmol) were dissolved in THF (75 mL) and flushed with N for 30 minutes. Simultaneously, an aqueous solution of K3PO4 (3 M, 7.66 mL, 23 mmol) was prepared and flushed with N2 for a minimum of 30 minutes. Tris(dibenzylideneacetone)dipalladium(0) (105 mg, 115 μmol) and tri-tert-butylphosphonium tetrafluoroborate (66.7 mg, 230 μmol) were added to the THF solution, which was then flushed with N2 for an additional 10 minutes. The degassed K3PO4 solution was charged to a flask, and the mixture was then placed in a preheated oil bath at 65 °C and stirred for 1 hour. Upon completion, the reaction was cooled and toluene (120 mL) was added. The organic layer was washed with water (2 x 60 mL) and then brine (120 mL). The combined organic extracts were dried over MgSO4, and the solvent was removed under reduced pressure to give intermediate 5 of compound 1 (6.03 g) as a waxy red solid. Due to the stability of the acetal group, the material was used directly in the next step without further purification. HPLC purity = 92.50%.

[0156] LCMS m / z 1541.1460[M+H] + . Intermediate 6 Intermediate 5 of compound 1 (3.56 g, 2.31 mmol) was dissolved in THF (165 mL). Water (32 mL) was added, followed by dropwise addition of trifluoroacetic acid (7.04 mL, 92.2 mmol). The reaction was warmed to 55° C. and stirred under N for 1 hour. The reaction was cooled to room temperature and then poured onto ice (150 g). A mixture of THF / n-heptane (4:1, 200 mL) was added, followed by portionwise addition of saturated NaHCO solution (approximately 100 mL, until the aqueous layer reached pH = 7). The organic layer was separated and washed with water (2 × 150 mL) and then brine (150 mL). The combined organic extracts were dried over MgSO, and the solvent was removed under reduced pressure to give a bright red oil. The crude material was purified by silica chromatography (heptane / toluene, 0 to 90% gradient elution) and then dried under vacuum for 18 hours to give compound 1 intermediate 6 (3.16 g, containing residual solvent) as a bright red viscous oil. HPLC purity = 95.94%.

[0157] 1 H NMR(600 MHz,CDCl3):δ [ppm] 9.73(s,2H),7.44(s,2H),7.30(s,2H),6.86(s,2H),6.81(s,4H),4.06(d,J=5.4 Hz,4H),2.47(t,J=7.9 Hz,8H),1.88(septet,J=6.1 Hz,2H),1.59-1.43(m,18H),1.38-1.33(m,8H),1.30-1.22(m,60H),0.88-0.82(m,26H). LCMS m / z 1367.9843 [M] + . Compound Example 1 IC-2CN was prepared as described in WO 2022 / 129137, the contents of which are incorporated herein by reference.

[0158] Intermediate 6 (500 mg, 365 μmol) of compound 1, IC-2CN (444 mg, 1.82 mmol), and p-toluenesulfonic acid (471 mg, 2.74 mmol) were dissolved in anhydrous toluene (18 mL) and absolute ethanol (36 mL). The mixture was flushed with N for 10 minutes, then warmed to 65 °C and stirred under N for 60 minutes. The reaction was cooled to room temperature and then concentrated under reduced pressure (leaving approximately 5 mL of residual solvent). Toluene (100 mL) was added, and the material was passed through a short silica plug (toluene / EtOAc, 95:5). The solvent was removed under reduced pressure, and the resulting crude material was purified by silica chromatography (heptane / dichloromethane, gradient elution 33 to 100%). The purified material was dissolved in a minimal amount of dichloromethane (approximately 5 mL) and precipitated into n-pentane (approximately 75 mL). The solid was collected by filtration and dried in a vacuum oven for 18 hours (50° C., 0.1 mbar) to give compound Example 1 (450 mg, 68%) as a deep blue solid. HPLC purity=90.63%.

[0159] 1H NMR(600 MHz,CDCl3):δ [ppm] 9.00(s,2H),8.77(s,2H),8.12(s,2H),7.67(s,2H),7.50(br s,2H),6.94(s,2H),6.81(s,4H),4.16(d,J=4.9 Hz,4H),2.51(t,J=7.9 Hz,8H),1.94(septet,J=5.8 Hz,2H),1.62-1.48(m,18H),1.42-1.36(m,8H),1.34-1.22(m,60H),0.90-0.79(m,26H). LCMS m / z 1820.9302 [M+H] + . UV-vis (1,2,4 trimethylbenzene) λ max (ε)951(212000), 847(101000), 310(47300)nm.

[0160] SWV (solution, toluene) HOMO = -5.30 eV; LUMO = -4.13 eV; E g =1.17 eV.

[0161] SWV (film, toluene) HOMO = -5.37 eV; LUMO = -4.28 eV; E g =1.19 eV.

[0162] Qx-2Cl [ka]

[0163] Step 1: Qx-2Cl intermediate 1 (250 g, 1.06 mol) was dissolved in 2.5 L of dichloroethane. N-Bromosuccinimide (754 g, 4.24 mol) was added portionwise to the reaction mixture, which was heated at 75° C. for 16 hours. Solid impurities were filtered off and washed with heptane. The filtrate was concentrated under vacuum to give 255 g of crude material. The product, Qx-2Cl intermediate 2, was used in the next step without further purification.

[0164] Step 2: Qx-2Cl intermediate 2 (99.9 g, 434 mmol) and Qx-2Cl intermediate 3 (55 g, 310 mmol) were dissolved in 1 L of ethanol. p-Toluenesulfonic acid (4.69 g, 24.7 mmol) was added to the reaction mixture and heated at 68 °C for 3 hours. The reaction was then concentrated in vacuo to give 105 g of crude product, which was purified by column chromatography using dichloromethane to give 80 g of the desired product.

[0165] Step 3: Qx-2Cl intermediate 4 (50 g, 134 mmol) was dissolved in 500 mL of methanol. Lithium hydroxide monohydride (12.9 g, 308 mmol) was added to the reaction mixture, which was then stirred at room temperature for 16 hours. The reaction mixture was filtered, and the resulting solid was stirred in dilute hydrochloric acid for 3 hours. The solid was filtered to give 30 g of the desired product, Qx-2Cl intermediate 5.

[0166] Step 4: Qx-2Cl intermediate 5 (30 g, 104 mmol) and acetic anhydride (600 mL) were combined in a flask. The reaction mixture was heated at 130° C. for 6 hours. After this time, it was cooled and concentrated under reduced pressure to give 30 g of crude product Qx-2Cl intermediate 6, which was used directly in the next step without further purification.

[0167] Process 5 To a stirred solution of Qx-2Cl intermediate 6 (30 g, 111 mmol) in acetic anhydride (240 mL) was added triethylamine (11.2 g, 111 mmol). To this was added tert-butyl acetoacetate (18.3 g, 116 mmol) dropwise. The reaction mixture was stirred at room temperature for 16 hours and then slowly poured into a separate flask containing 1.5 N hydrochloric acid (400 mL) and 400 mL of ice water. This was then stirred at room temperature for 48 hours. The resulting solid was isolated by filtration to give 15 g of the desired product, Qx-2Cl intermediate 7, as a black solid, which was used in the next step without further purification.

[0168] Process 6 Qx-2Cl intermediate 7 (5 g, 18.7 mmol) was dissolved in pyridine (90 ml). Malononitrile (3.08 g, 46.7 mmol) was added, and the mixture was stirred at room temperature for 2 hours. The reaction was concentrated under reduced pressure to give 9 g of crude material, which was purified by neutral alumina column chromatography using dichloromethane and 1% triethylamine in methanol. The resulting product was triturated with hexane / dichloromethane and filtered to give 2.013 g of pure Qx-2Cl product (98.81% by HPLC) as the triethylamine salt.

[0169] Compound Example 2 [ka]

[0170] Intermediate 6 (360 mg, 263 μmol), Qx-2Cl (412 mg, 1.31 mmol), and p-toluenesulfonic acid (339 mg, 1.97 mmol) were dissolved in anhydrous toluene (13 mL) and absolute ethanol (26 mL). The mixture was flushed with N for 10 minutes, then warmed to 65 °C and stirred under N for 90 minutes. Upon completion, the hot reaction mixture was filtered, and the remaining solid was washed with hot MeOH (2 × 20 mL), hot EtOH (2 × 20 mL), and pentane (2 × 20 mL). The solid was dried on the filter paper under a N shower. The solid was purified by silica chromatography (heptane / dichloromethane, gradient elution 33% to 100%). The purified material was dissolved in a minimal amount of dichloromethane (approximately 5 mL) and precipitated into MeOH (approximately 75 mL). The solid was collected by filtration and dried in a vacuum oven for 18 hours (50° C., 0.1 mbar) to give compound Example 2 (324 mg, 63%) as a deep blue solid. HPLC purity=97.19%.

[0171] 1H NMR (600 MHz, CDCl): δ [ppm] 8.82 (br s, 2H), 8.47 (s, 2H), 8.39 (s, 2H), 7.70 (s, 2H), 6.95 (s, 2H), 6.81 (s, 4H), 4.19 (d, J = 4.3 Hz, 4H), 2.53 (t, J = 7.9 Hz, 8H), 1.96 (septet, J = 6.1 Hz, 2H), 1.63-1.48 (m, 18H), 1.43-1.36 (m, 8H), 1.36-1.20 (m, 58H), 0.90-0.80 (m, 24H). Note: Not all resonances are observed due to overlapping signals.

[0172] LCMS m / z 1961.9491[M] - ,1977.9491[M+NH4] + . UV-vis (1,2,4 trimethylbenzene) λ max (ε)978(233000),873(94700),779(30600)nm. SWV (solution, toluene) HOMO = -5.33 eV; LUMO = -4.24 eV; E g =1.09 eV. SWV (film, toluene) HOMO = -5.53 eV; LUMO = -4.22 eV; E g =1.31 eV. Compound Example 3 [ka]

[0173] Compound Example 3, Intermediate 2 Compound 3, Intermediate 1 (3.05 g, 7.57 mmol) was dissolved in anhydrous THF (120 mL) and then cooled to −78° C. The mixture was flushed with N for 15 minutes. n-Butyllithium (2.5 M in hexanes, 6.32 mL, 15.8 mmol) was added dropwise to the mixture so that the internal temperature did not exceed −70° C. The reaction was stirred at −78° C. for 90 minutes, then slowly warmed to 0° C. and left stirring at this temperature for an additional hour. The reaction was cooled to −78° C., then neat tributyltin chloride (6.32 mL, 15.8 mmol) was added dropwise so that the internal temperature did not exceed −70° C. The reaction was stirred at −78° C. for an additional hour, then warmed to room temperature and stirred for an additional 16 hours. The reaction was cooled to 0° C. and quenched by the addition of water (75 mL). The organic layer was extracted with n-heptane (100 mL) and then washed with water (3 x 75 mL) and saturated brine (75 mL). The organic extract was dried over MgSO4 and the solvent removed under reduced pressure to give compound 3, intermediate 2, as a pale yellow oil (8.38 g, 112% containing excess Bu3SnCl). The material was used directly in the next step without further purification. HPLC purity = 34.58% - note that this is a complex mixture of tin-containing species.

[0174] LCMS m / z 981.5079[M+H] + . Compound Example 3 Intermediate 4 Compound Example 3, Intermediate 2 (2.62 g, 2.67 mmol) and Compound Example 3, Intermediate 3 (3.03 g, 5.87 mmol) were dissolved in anhydrous toluene (55 mL) and flushed with N for 15 minutes. Tris(dibenzylideneacetone)dipalladium(0) (195 mg, 214 μmol) and tris(o-tolyl)phosphine (243 mg, 801 μmol) were added to the flask, and the mixture was flushed with N for an additional 5 minutes. The mixture was heated to 110 °C and stirred under N for 1 hour. The cooled reaction mixture was passed through a silica plug, washed first with n-heptane (the filtrate was discarded), and then with n-heptane / dichloromethane (1:1). The solvent was removed under reduced pressure to give Compound Example 3, Intermediate 4 (6.17 g, 180%, containing excess Intermediate 3 and tin-containing species) as a viscous red oil. HPLC purity = 52.54%.

[0175] LCMS m / z 1275.9453[M+H] + . Compound Example 3 Intermediate 5 Compound Example 3 Intermediate 4 (3.50 g, 2.74 mmol) was dissolved in THF (195 mL). Water (39 mL) was added, followed by the dropwise addition of trifluoroacetic acid (3.77 mL, 49.3 mmol). The reaction was warmed to 55° C. and stirred under N for 2.5 hours. The reaction was cooled to room temperature and then poured onto ice (200 g). A mixture of THF / n-heptane (4:1, 200 mL) was added, followed by the portionwise addition of saturated NaHCO solution (approximately 75 mL, until the aqueous layer reached pH=7). The organic layer was separated and washed with water (2×150 mL) and then brine (150 mL). The combined organic extracts were dried over MgSO, and the solvent was removed under reduced pressure to give a bright red oil. The crude material was purified by silica chromatography (heptane / dichloromethane, gradient elution 0 to 100%) to give compound Example 3 Intermediate 5 (1.98 g, 66%) as a bright red viscous oil. HPLC purity=93.95%.

[0176] 1 H NMR(600 MHz,CDCl3):δ [ppm] 9.77(s,2H),7.49(s,2H),7.36(s,2H),4.11(t,J=5.2 Hz,4H),1.93(dq,J=10.4,5.2 Hz,6H),1.65-1.58(m,4H),1.55-1.48(m,4H),1.45-1.25(m,50H),1.06-0.97(m,11H),0.97-0.87(m,23H),0.73(t,J=6.1 Hz,8H),0.64(t,J=7.2 Hz,6H). LCMS m / z 1103.7786 [M+H] + . Compound Example 3 Compound Example 3: Intermediate 5 (445 mg, 403 μmol), Qx-2Cl (633 mg, 2.01 mmol), and p-toluenesulfonic acid (520 mg, 3.02 mmol) were dissolved in anhydrous toluene (40 mL) and absolute ethanol (15 mL). The mixture was flushed with N for 10 minutes, then warmed to 65° C. and stirred under N for 60 minutes. Upon completion, the hot reaction mixture was filtered, and the remaining solid was washed with hot MeOH (2×30 mL), hot EtOH (2×30 mL), and pentane (2×30 mL). The solid was dried on the filter paper under a N shower. The solid was dried in a vacuum oven for 18 hours (50° C., 0.1 mbar) to give Compound Example 3 (592 mg, 87%) as a deep blue solid. HPLC purity = 89.61%.

[0177] 1 H NMR (600MHz, toluene-d8): δ [ppm] 8.81(s,2H),8.17(s,2H),8.00(t,J=5.3 Hz,2H),7.82(t,J=11.2 Hz),7.45(br s,2H),3.81(s,4H),1.99(dq,J=11.5,4.2 Hz,4H),1.86-1.77(m,2H),1.68-1.60(m,4H),1.77-1.52(m,4H),1.49-1 .36(m,39H),1.21-1.10(m,10H),1.10-1.01(m,12H),0.99(dt,J=5.7,1.2 Hz,6H),0.91(dt,J=6.9,1.3 Hz,6H),0.89-0.84(m,2H),0.78(t,J=7.4 Hz,6H). LCMS m / z 1698.6919[M+H] + . UV-vis (1,2,4-trimethylbenzene) λ max (ε)983(233000), 880(92300), 785(29400).

[0178] SWV (solution, toluene) HOMO = -5.27 eV; LUMO = -4.25 eV; E g =1.02 eV.

[0179] SWV (film, toluene) HOMO = -5.48 eV; LUMO = -4.23 eV; E g =1.25 eV.

[0180] Model Data The energy levels of the exemplary compounds were modeled using Gaussian09 software available from Gaussian using Gaussian09 with B3LYP (function). The results are shown in Table 1, where S1f corresponds to the oscillator strength of the transition from S1 (predicting absorption intensities). [Table 5] TIFF2026506000000046.tif115155 [Table 6] TIFF2026506000000048.tif51154 [Table 7] [Table 8] [Table 9] TIFF2026506000000052.tif233157

Claims

1. Formula (I): 【Chemistry 1】 A compound of the formula: X １ is C(R １ ) ２ , Si(R １ ) ２ or Ge(R １ ) ２ where R １ is, in each occurrence, a substituent; Y １ is O, S or Se, Ar １ is independently in each occurrence an unsubstituted or substituted monocyclic or polycyclic aryl or heteroaryl group, or is absent; B １ is, independently in each occurrence, a bridging group; f1 and f2 are each 1; g is at least 1; A in each occurrence is independently a monovalent electron-withdrawing group; A compound of formula (I).

2. At least one A is of formula (II): 【Chemistry 2】 is an electron-withdrawing group of the formula: G is C=O, C=S SO, SO ２ , N.R. ３３ or C(R ３３ ) ２ where R ３３ is CN or COOR ４０ where R ４０ is H or a substituent group in each occurrence; R ３ is H or a substituent, Z is independently CN, CF ３ or COOR ４０ where R ４０ is H or a substituent group in each occurrence; Ar ２ 10. The compound of claim 1, wherein is an unsubstituted or substituted monocyclic or polycyclic aromatic or heteroaromatic ring.

3. Ar ２ but, benzene substituted with at least one CN substituent; and unsubstituted or substituted monocyclic or polycyclic heteroaromatic groups 3. The compound of claim 2, selected from:

4. The group of formula (II) is of formula (IIa): 【Transformation 3】 wherein each X ７ ~X １０ is an independent CR １２ or N, and R １２ is H or C in each occurrence １～２０ is a substituent selected from hydrocarbyl and electron-withdrawing groups, provided that X ７ ~X １０ Each of these is CR １２ If at least one R １２ is CN, The compound of claim 3.

5. When the group of formula (II) is a group of formula (IIb): 【Chemistry 4】 wherein Ar ３ is an unsubstituted or substituted monocyclic or polycyclic aromatic or heteroaromatic group, The compound of claim 3.

6. Ar ２ The compound of claim 3, wherein is unsubstituted or substituted benzene.

7. B １ The compound of any one of claims 1 to 6, wherein is selected from unsubstituted or substituted furan; unsubstituted or substituted thiophene; or fused analogues thereof.

8. B １ is of formula (III): 【Transformation 5】 is a group of the formula ２ is O, S or Se, and Ar ４ is an unsubstituted or substituted monocyclic or polycyclic aromatic or heteroaromatic group, The compound of claim 7.

9. Ar ３ is of formula (IIIa): 【Transformation 6】 where R ８ is H or a substituent group at each occurrence; The compound of claim 8.

10. A composition comprising the compound according to any one of claims 1 to 9 and an electron donating material.

11. A formulation comprising a compound or composition according to any one of claims 1 to 10 dissolved or dispersed in one or more solvents.

12. 11. An organic photoresponsive device comprising an anode, a cathode, and a photoactive layer disposed between the anode and the cathode, the photoactive layer comprising the composition of claim 10.

13. 13. A light sensor comprising: a light source; and the organic photodetector of claim 12, wherein the organic photodetector is configured to detect light emitted from the light source.

14. The optical sensor of claim 13 , wherein the light source emits light having a peak wavelength greater than 1000 nm.

Images